Bromonitrothienyldioxanes

Abstract

The invention relates to novel 5-bromo-5-nitro-2-thienyl-1,3-dioxanes of the formula (I) in which R 1 , R 2 and R 3 are as defined in the description are highly suitable for use as biocides for protecting plants and industrial materials.

What is claimed is:  
     
         1 . A 5-bromo-5-nitro-2-thienyl-1,3-dioxane of the formula (I)  
       
         
           
           
               
               
           
         
         wherein R 1 , R 2  and R 3  independently of one another represent hydrogen, halogen, nitro, cyano, or represent in each case an optionally substituted alkyl, alkenyl, alkynyl, acyl, acyloxy, alkoxy, alkoxycarbonyl, alkylthio, amino, mono- or dialkylamino group.  
       
     
     
         2 . The compound according to  claim 1 , wherein in formula (I), R 1 , R 2  and R 3  independently of one another represent (1) hydrogen, (2) halogen, (3) cyano, (4) nitro, or (5) a straight-chain or branched C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl or C 2 -C 8 -alkynyl, which are in each case optionally mono- or polysubstituted by identical or different substitutents from the group consisting of halogen, nitro, and cyano groups, C 1 -C 6 -alkoxy which is optionally mono- to nonasubstituted by identical or different halogens and C 1 -C 6 -alkylthio which is optionally mono- to nonasubstituted by identical or different halogens, or (6) a C 1 -C 6 -acyl, (7) a C 1 -C 6 -acyloxy, (8) a C 1 -C 6 -alkoxycarbonyl which is optionally mono- or disubstituted by identical or different halogens, (9) a C 1 -C 5 -alkoxy, which is optionally mono- to hexasubstituted by identical or different halogens, (10) a C 1 -C 5 -alkylthio, which is optionally mono- to hexasubstituted by identical or different halogens, or (11) an amino group, (12) a monoalkylamino group having straight-chain or branched C 1 -C 6 -alkyl radicals or (13) a dialkylamino group having identical or different straight-chain or branched C 1 -C 6 -alkyl radicals.  
     
     
         3 . A process for preparing a 5-bromo-5-nitro-2-thienyl-1,3-dioxane of the formula (I)  
       
         
           
           
               
               
           
         
         wherein R 1 , R 2  and R 3  independently of one another represent hydrogen, halogen, nitro, cyano, or represent in each case an optionally substituted alkyl, alkenyl, alkynyl, acyl, acyloxy, alkoxy, alkoxycarbonyl, alkylthio, amino, mono- or dialkylamino group,  
         the process comprising: 
 A) reacting, in a transacetalization reaction, 2-bromo-2-nitropropane-1,3-diol (bronopol) with an acetal of the general formula (III)  
                     
  wherein R 1 , R 2  and R 3  are independently of one another represent  
 hydrogen, halogen, nitro, cyano, or represent in each case an optionally substituted alkyl, alkenyl, alkynyl, acyl, acyloxy, alkoxy, alkoxycarbonyl, alkylthio, amino, mono- or dialkylamino group, and  
 
         R 4  represents alkyl, optionally in the presence of a catalyst and optionally, in the presence of a diluent.  
       
     
     
         4 . The process of  claim 3 , wherein the process is carried out at a temperature ranging from about 10 to about 180° C.  
     
     
         5 . The process of  claim 3 , wherein the process is carried out at a temperature ranging from about 20 and 145° C.  
     
     
         6 . A compound of the formula (III):  
       
         
           
           
               
               
           
         
         wherein R 1 , R 2  and R 3  are independently of one another represent  
         hydrogen, halogen, nitro, cyano, or represent in each case an optionally substituted alkyl, alkenyl, alkynyl, acyl, acyloxy, alkoxy, alkoxycarbonyl, alkylthio, amino, mono- or dialkylamino group, and  
         R 4  represents alkyl.  
       
     
     
         7 . A process for preparing a compound of formula (III)  
       
         
           
           
               
               
           
         
       
       comprising: 
 (A) reacting (1) an aldehyde of the general formula (II)  
                     
 wherein R 1 , R 2  and R 3  are independently of one another represent hydrogen, halogen, nitro, cyano, or represent in each case an optionally substituted alkyl, alkenyl, alkynyl, acyl, acyloxy, alkoxy, alkoxycarbonyl, alkylthio, amino, mono- or dialkylamino group, with 
 (2) an alcohol of the formula (IV),  
                     
 wherein R 4  represents alkyl,optionally in the presence of a catalyst, optionally in the presence of a dehydrating agent if appropriate, in a diluent.  
 
 
     
     
         8 . The process of  claim 7 , wherein the process is carried out at a temperature ranging from about 10 to about 180° C.  
     
     
         9 . The process of  claim 7 , wherein the process is carried out at a temperature ranging from about 20 and 145° C.  
     
     
         6 .  10 . A method comprising treating an industrial material with a 5-bromo-5-nitro-2-thienyl-1,3-dioxane of the formula (I)  
       
         
           
           
               
               
           
         
       
       wherein R 1 , R 2  and R 3  independently of one another represent hydrogen, halogen, nitro, cyano, or represent in each case an optionally substituted alkyl, alkenyl, alkynyl, acyl, acyloxy, alkoxy, alkoxycarbonyl, alkylthio, amino, mono- or dialkylamino group, and thereby protecting the industrial material against attack and destruction from an microorganism.  
     
     
         11 . The method of claim  10 , wherein the 5-bromo-5-nitro-2-thienyl-1,3-dioxane of the formula (I) is applied in an amount ranging from about 0.01 to about 5% by weight, based on the engineered material.  
     
     
         12 . The method of claim  10 , wherein the 5-bromo-5-nitro-2-thienyl-1,3-dioxane of the formula (I) is applied in an amount ranging from about 0.05 to about 1% by weight, based on the engineered material.  
     
     
         13 . The method of claim  10 , wherein the industrial material is selected from the group consisting of paints, leather, wood, plastics, cooling lubricants, and combinations thereof.  
     
     
         14 . A method comprising treating a plant substrate, a seed substrate, or a soil substrate with a 5-bromo-5-nitro-thienyl-1,3-dioxane of the formula (I):  
       
         
           
           
               
               
           
         
         wherein R 1 , R 2  and R 3  independently of one another represent hydrogen, halogen, nitro, cyano, or represent in each case an optionally substituted alkyl, alkenyl, alkynyl, acyl, acyloxy, alkoxy, alkoxycarbonyl, alkylthio, amino, mono- or dialkylamino group, and thereby protecting the plant against attack and destruction from an microorganism.  
       
     
     
         15 . The method of  claim 14 , wherein the 5-bromo-5-nitro-thienyl-1,3-dioxane of the formula (I) is applied in an amount ranging from about 0.1 to about 10,000 ga/hr.  
     
     
         16 . The method of  claim 14 , wherein the 5-bromo-5-nitro-thienyl-1,3-dioxane of the formula (I) is applied in an amount ranging from about 10 to about 1,000 ga/hr.  
     
     
         17 . A microbicidal formulation comprising: 
 (A) a 5-bromo-5-nitro-2-thienyl-1,3-dioxane of the formula (I)                          wherein R 1 , R 2  and R 3  independently of one another represent hydrogen, halogen, nitro, cyano, or represent in each case an optionally substituted alkyl, alkenyl, alkynyl, acyl, acyloxy, alkoxy, alkoxycarbonyl, alkylthio, amino, mono- or dialkylamino group,    (B) at least one solvent or diluent, and    (C) optionally, a processing auxiliary or an additional antimicrobially active compound.    
     
     
         18 . The formulation according to  claim 17 , wherein the additional antimicrobially active compound is selected from the group consisting of fungicides, bactericides, acaricides, nematicides, algicides, insecticides, and mixtures thereof.  
     
     
         19 . The formulation of  claim 17 , wherein the formulation comprises from about 0.1 to about 95% by weight of active compounds, based on the total weight of the formulation.  
     
     
         20 . The formulation of  claim 17 , wherein the formulation comprises from about 0.5 to about 90%, based on the total weight of the formulation.  
     
     
         21 . An industrial material comprising a substrate containing 
 a 5-bromo-5-nitro-2-thienyl-1,3-dioxane of the formula (I)                          wherein R 1 , R 2  and R 3  independently of one another represent hydrogen, halogen, nitro, cyano, or represent in each case an optionally substituted alkyl, alkenyl, alkynyl, acyl, acyloxy, alkoxy, alkoxycarbonyl, alkylthio, amino, mono- or dialkylamino group,